CN110112368A - The plasma pretreatment of current-collector for thin film lithium metallization - Google Patents
The plasma pretreatment of current-collector for thin film lithium metallization Download PDFInfo
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- CN110112368A CN110112368A CN201910068579.8A CN201910068579A CN110112368A CN 110112368 A CN110112368 A CN 110112368A CN 201910068579 A CN201910068579 A CN 201910068579A CN 110112368 A CN110112368 A CN 110112368A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0419—Methods of deposition of the material involving spraying
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides the methods for being used to form lithium base cathode component.The surface of metal collector is handled with Reductive plasma gas, so that the processing surface of the metal collector is formed to have the contact angle less than or equal to about 10 °, and has the metal oxide less than or equal to about 5% after the processing step.The metal collector may include the metal of such as copper, nickel and iron.Lithium metal is applied to the processing surface of metal collector in the environment for being substantially free of oxide matter.Lithium metal flows through and is attached to the processing surface, to form lithium layer.The lithium layer can be thickness >=about 1 μm≤about 75 μm thin layer, to form lithium an- ode component.
Description
Introduction
This part, which provides, is related to background information of the invention, the not necessarily prior art.
The present invention relates to formed by carrying out lithium metal after corona treatment metal collector again for electrification
The method for learning the lithium base cathode component of battery.
The high-energy density electrochemical cell of such as lithium ion battery can be used in various consumer products and vehicle, example
Such as, hybrid electric vehicles (HEV) and electric vehicle (EV).Typical lithium ion battery and lithium-sulfur cell include first electrode, the
Two electrodes, electrolyte and diaphragm.One electrode is used as anode or cathode (when electric discharge), and another is used as cathode or anode
(when electric discharge).One group of battery can be electrically connected, to improve overall output.Traditional rechargeable lithium ion batteries pass through in cathode
Transmit lithium ion reversibly back and forth between anode to operate.Diaphragm and electrolyte are arranged between cathode and anode.Electrolyte
Suitable for conducting lithium ions, and it can be solid (for example, solid-state diffusion) or liquid form.Lithium ion is during battery charges
It is moved to anode (cathode) from cathode (anode), and is moved in a reverse direction in battery discharge.
Many different materials are used equally for manufacture for the component of lithium ion battery.Common negative electrode material includes that lithium is inserted
Enter material or alloy bulk material, such as carbon-based material, for example, lithium-graphite intercalation compound, lithium-silicon compound, lithium-tin alloy
With lithium titanate Li4+xTi5O12, wherein 0≤x≤3, such as Li4Ti5O12(LTO).Cathode also (can be often referred to lithium metal by lithium metal
Anode (LMA)) it is made, therefore electrochemical cell is considered as lithium metal battery.The lithium metal of cathode for rechargeable battery
It is minimum with various potential advantages, including theoretical capacity highest, electrochemical potential.Therefore, the battery containing lithium anodes can have
Have the higher energy density that can potentially make memory capacity double so that battery can be halved with size, but still with its
Its lithium ion battery continues the identical time.Therefore, lithium metal battery is one of most promising candidate of high energy storage system.
However, lithium metal battery can potentially show unreliable or reduced performance, cause to may be decreased electrochemistry
The service life of battery.The problem generated is that lithium metal level of reactivity is high, this may cause interfacial instability and lithium
Metal is exposed to various substances during the manufacture and operation of electrochemical cell and undesirable reaction occurs (for example, it may be possible to cause
The formation of dendrite).Another potential cause of lithium metal battery performance decline may be with lithium metal and metal collector
Long-term weak caking property is related, and when using lithium base cathode in electrochemical cell, this will cause passage resistance and impedance at any time
Undesirable increase can be generated.As a result, it is desirable to research and develop for the reliable, high performance containing lithium of high-energy electrochemical cell
Negative electrode material, can be minimized passage at any time and caused by reduced performance (caused for example, minimizing because of long-time service
Resistance/impedance increase and capacity attenuation)
Summary of the invention
This part provides substantially summary of the invention of the invention, but is not the comprehensive of its full scope or its all feature
It is open.
In all fields, the present invention provides a kind of methods for being used to form lithium base cathode.This method includes using reproducibility
Plasma gas handles the surface of metal collector, so that forming the metal collector after the processing step
Processing surface.The processing surface can have the contact angle less than or equal to about 10 °, and have less than or equal to about 5%
Metal oxide.Metal in metal collector is selected from the group being made of the following terms: copper (Cu), nickel (Ni), iron (Fe), and
A combination thereof.This method further includes the processing table that lithium metal is applied to metal collector in the environment for being substantially free of oxide matter
Face.Lithium metal flows through and is attached to the processing surface, to form thickness greater than or equal to about 1 micron (μm) to less than or be equal to about
75 μm of lithium layer, to form lithium an- ode.
On the one hand, which includes the molecule selected from the group being made of the following terms: argon (Ar),
Nitrogen (N2), hydrogen (H2), ammonia (NH3), and combinations thereof.
On the one hand, the step of being handled with the Reductive plasma gas the surface uses selected from by the following terms
The plasma source of the group constituted: high energy plasma, the low pressure plasma, induction generated by microwave plasma source
Coupled plasma, and combinations thereof.
On the one hand, after the treatment step and before application step, metal collector setting is greater than or equal in temperature
About 50 DEG C to less than or the warm table equal to about 120 DEG C on.
On the one hand, processing step and application step carry out in same reaction chamber.
On the one hand, the step of being handled with surface of the Reductive plasma gas to metal collector with by
High energy plasma caused by 13.56MHz radio frequency (RF) plasma source or 2.48GHz microwave plasma source carries out.
On the one hand, current-collector is film or foil.The thickness of current-collector greater than or equal to about 2 microns (μm) to less than or can be equal to
About 30 μm.The lithium metal for being applied to the processing surface of metal collector can be thickness greater than or equal to about 5 μm to less than or wait
In about 75 μm of lithium film or foil.
On the one hand, during at least part for applying step, pressure is applied to the lithium layer.
In all fields, the present invention provides a kind of method for forming lithium an- ode, this method includes with reproducibility etc.
Plasma gas handles the surface of the current-collector containing copper.After the treatment step, the processing surface of current-collector has
Contact angle less than or equal to about 10 °, and there is the Cu oxide less than or equal to about 5%.This method further includes will have
The current-collector on the processing surface is heated to greater than or equal to about 50 DEG C to less than or the temperature equal to about 120 DEG C.It is being substantially free of
Lithium metal is applied to the processing surface of current-collector by oxidation material and water content in the environment less than or equal to about 1 mass %.
Lithium metal flows through and is attached to the processing surface, to form lithium layer.The thickness of the lithium layer can be greater than or equal to about 1 micron (μm) extremely
Less than or equal to about 75 μm, to form lithium an- ode.
On the one hand, which includes the molecule selected from the group being made of the following terms: argon (Ar),
Nitrogen (N2), hydrogen (H2), ammonia (NH3), and combinations thereof.
On the one hand, the step of being handled with the Reductive plasma gas the surface uses selected from by the following terms
The plasma source of the group constituted: energetic plasma, low pressure plasma, the induction coupling generated by microwave plasma source
Plasma is closed, and combinations thereof.
On the one hand, processing step and application step carry out in same reaction chamber.
On the one hand, the step of being handled with surface of the Reductive plasma gas to metal collector with by
High energy plasma caused by 13.56MHz radio frequency (RF) plasma source or 2.48GHz microwave plasma source carries out.
On the one hand, current-collector is thickness greater than or equal to about 2 μm to less than or lithium film or foil equal to about 30 μm.In addition,
The lithium metal for being applied to the processing surface of metal collector is lithium film or foil, thickness can greater than or equal to about 5 μm to less than or
Equal to about 75 μm.
On the one hand, during at least part for applying step, pressure is applied to the lithium layer.
In other other aspects, the present invention provides a kind of lithium base cathode components.The component includes having processing table
The metal collector in face, which has the contact angle less than or equal to about 10 °, and has less than or equal to about 5%
Metal oxide.Metal in metal collector is selected from the group being made of the following terms: copper (Cu), nickel (Ni), iron (Fe),
And combinations thereof.The component further includes setting in thickness greater than or equal to about 1 micron (μm) to less than or processing equal to about 75 μm
Lithium metal layer on surface.Compared with the comparison interface between lithium metal and the metal collector without handling surface, table is handled
The nucleation overpotential at the interface limited between face and lithium metal layer is reduced more than or is equal to 10%.
On the one hand, metal collector includes copper, and handles surface with the Cu oxide less than or equal to about 5%.
According to descriptions provided herein, other application field be will become obvious.Description in the content of present invention
For illustration purposes only with specific example, it is not intended to limit the scope of the present invention.
Detailed description of the invention
Drawings described herein is merely for the purpose for showing selected embodiment, and not all possible embodiment party
Case, and be not intended to limit the scope of the invention.
Fig. 1 show some aspects according to the present invention for Reductive plasma gas carrying out pretreated show
Example property plasma reactor.
Fig. 2 shows the exemplary sectional views for the lithium base cathode component that some aspects according to the present invention are formed.
Fig. 3 shows the surface layer component for determining the copper foil of corona treatment of some aspects preparation according to the present invention
With x-ray photoelectron spectroscopy (XPS) figure with depth section of thickness.
Fig. 4 shows the first battery of the lithium base cathode component formed comprising some aspects according to the present invention and comprising not
Carry out the second battery performance (voltage (V)) comparison that (hour) elapses at any time of the lithium base cathode of any corona treatment.
In all the appended drawings, corresponding appended drawing reference indicates corresponding component.
Specific embodiment
There is provided herein exemplary embodiments, therefore the present invention will become completely, and will be completely by the scope of the present invention
It is conveyed to those skilled in the art.Many details (for example, concrete component, the example of components, apparatus, and method) is proposed,
To provide the thorough understanding to the embodiment of the present invention.It will be readily apparent to one skilled in the art that not needing using tool
Body details, exemplary embodiment can be embodied in many different forms, and be not necessarily to be construed as limiting model of the invention
It encloses.In some of the exemplary embodiments, already known processes, known devices structure and known technology are not described in detail.
Term as used herein and is not intended to restricted merely for the purpose of description certain exemplary embodiments
's.As used herein, singular "one", "the" can be intended to also include plural form, unless separately having in context
It clearly states.Term " includes " "comprising" " having " is inclusiveness, therefore shows that there are the feature, element, component, steps
Suddenly, entirety, operation and/or component, but one or more of the other feature, entirety, step, operation, component, assembly unit is not precluded
And/or combination thereof presence or addition.Although open term " comprising " is interpreted as describing and being claimed this paper institute
The non-limiting term of each embodiment proposed, but in some aspects, which can alternatively be interpreted as more limiting
The term of property and limitation, such as " by ... form " or "consisting essentially of".Therefore, for describing component, material, portion
For part, element, feature, entirety, any given embodiment of operation and/or processing step, the present invention also specifically include by or
Substantially the embodiment that forms of the component described in this class, material, component, element, feature, entirety, operation and/or processing step.?
" by ... form " in the case where, alternate embodiment does not include any other component, material, component, element, feature, entirety, behaviour
Make and/or processing step, and in the case where " substantially by ... form ", such embodiment does not include substantial influences substantially
With any other component, material, component, element, feature, entirety, operation and/or the processing step of novel characteristics, but the implementation
May include in example can't substantially influence substantially with any component of novel characteristics, material, component, element, feature, whole
Body, operation and/or processing step.
Any method and step, technique and operation described herein is not construed as necessarily requiring with described or shown specific
Sequence carries out, unless explicitly stated otherwise progress sequence.It should also be understood that unless otherwise specified, other or substitution step otherwise can be used
Suddenly.
If component, element or layer refer to " on another element or layer ", " being bonded to another element or layer ", " connection
To another element or layer " or " being attached to another element or layer ", then it can be directly in another component, element or layer
Above, another component, element or layer are bonded directly to or is attached directly to another component, element or layer, or also may be present
Intermediary element or layer.On the contrary, when element refers to " directly on another element or layer ", " be spliced directly to another element or
Layer ", " being connected directly to another element or layer " or when " being attached directly to another element or layer ", can be not present cental element
Part or layer.Other words for describing relationship between element should explain in an identical manner (for example, " ... between "
With " located immediately at ... between ", " adjacent " and " direct neighbor " etc.).As used herein, term "and/or" includes phase
Close any and all combinations of one or more of listed item.
Although term first, second, third, etc. can be used herein to describe each step, component, assembly unit, region, layer
And/or part, but these steps, component, assembly unit, regions, layers, and/or portions should not be limited by these terms, unless
It is otherwise noted.These terms can only be used to by a step, component, assembly unit, region, layer or part with another step, element,
Component, region, layer or part distinguish.Unless clearly indicated by the context, otherwise such as " first " used herein, "
Two " and the terms of other numerical terms do not imply that order or sequence.Therefore, the introduction for not departing from exemplary embodiment the case where
Under, the first step that is discussed below, component, assembly unit, region, layer or part can be referred to as second step, component, assembly unit, region,
Layer or part.
Herein can be used such as " before ", " later ", " inside ", " outside ", " under ", " lower section ", " lower end ", " it
On ", the space of " upper end " etc. or time relative terms, to describe the pass of an elements or features and another elements or features
System, as shown in the picture.Other than direction shown in figure, space or time relative terms can be intended to include device or system
Different directions in use or operation.
In the content of the present invention, numerical value indicate approximate measure, or by scope limitation be include given value it is small partially
Difference and the embodiment with described value and the exact value with described value.In addition to what is provided at the end of specific embodiment
Except Working Examples, all numerical value of the parameter (for example, quantity or condition) in this specification (including appended claims) are equal
It is interpreted as being modified by term " about " in all cases, before no matter whether " about " word really appear in numerical value." about " it indicates
The numerical value allows to have some slight inaccurate (numerically close to exact value；Substantially or the fairly close numerical value；Almost
The numerical value).If in the art not with this ordinary meaning understand " about " provided by inexactness, institute herein
" about " used at least indicates the modification that can be generated by measuring and using the commonsense method of these parameters.For example, " about " can
Including be less than or equal to 5% variation, be alternatively less than or be equal to 4%, be alternatively less than or be equal to 3%, be alternatively less than or
Equal to 2%, be alternatively less than or be equal to 1%, be alternatively less than or be equal to 0.5%, and in some aspects, be alternatively less than or
Equal to 0.1%.
In addition, the disclosure of range include all values and in entire scope further division range, including endpoint and
The subrange given for range.
Exemplary embodiment is described in more detail with reference to the drawings.
The invention proposes it is a kind of manufacture for electrochemical cell electrode assembly (e.g., including electroactive material layer
Cathode and metal collector) method.For example, electrochemical cell may include battery, capacitor or supercapacitor.Properly
Battery may include lithium ion, lithium sulphur and lithium lithium Symmetrical cells.The high-energy density electrochemical cell of such as lithium-base battery can be with
In various consumer products and vehicle.As non-limiting example, the example that the device of electrochemical cell can be used includes
For the motor of hybrid vehicle or fully-automatic vehicle, laptop computer, tablet computer, cellular phone and radio
Power driven tools or utensil.
In some aspects, therefore, the present invention provides the methods for forming lithium base cathode.Lithium base cathode be include metal current collection
The component of device and the electroactive lithium metal layer being arranged on the surface of metal collector.Metal in metal collector optionally selects
The group that free the following terms is constituted: copper (Cu), nickel (Ni), iron (Fe), alloy, and combinations thereof.For example, current-collector can be by
The ferroalloy of such as stainless steel is formed.Copper and mickel is the particularly challenging metal base for being formed on lithium metal layer,
Because they do not react at room temperature with lithium usually and have significant nucleation overpotential.In addition, these metals have
The tendency for forming metal oxide, can further suppress the formation of the uniform lithium metal layer with good adhesion.
Current techniques for forming lithium metal layer on this metalloid current-collector include with strong solvent (for example, toluene, third
Ketone etc.) and strong acid (for example, sulfuric acid) handled, generally include multiple cumbersome processing steps.However, even with such skill
After art is handled, a large amount of metal oxide is still likely to remain on treated current collector surface, to reduce
Wetability of the lithium metal on current collector surface, this finally will affect bonded between lithium metal and metal collector surface it is potential
Intensity.Nucleation overpotential will not be reduced to required degree by such technology.Furthermore, it is necessary to which thicker lithium layer ensures that surface is covered
Cover degree is uniform.If the lithium applied to current-collector is uneven and/or bonding between lithium metal and current-collector is insecure,
So over time, the resistance of cathode and/or impedance can increase.
Therefore, various aspects according to the present invention, this method are needed with Reductive plasma gas to metal collector
Surface handled.As described in more detail below, plasma energy source can produce plasma-based reducibility gas.
In some aspects, which has the component including one or more reducing agents or inert molecule, such as
Molecule selected from the group being made of the following terms: argon (Ar), nitrogen (N2), hydrogen (H2), ammonia (NH3), and combinations thereof.It is such as following
It further discusses, oxidation material may be not present in Reductive plasma gas.With the Reductive plasma gas
The step of handling the surface uses the plasma source selected from the group being made of the following terms: by microwave plasma
Energetic plasma, the low pressure plasma, inductively coupled plasma of source generation, and combinations thereof.It is as follows in a kind of modification
What text further described, the step of being handled with surface of the Reductive plasma gas to metal collector with by
Energetic plasma caused by 13.56MHz radio frequency (RF) plasma source or 2.48GHz microwave plasma source carries out.
Reaction gas containing plasma is the gas with free electron, cation and other chemical substances, is passed through
Increase surface energy and improves wettability and caking ability to reduce energy barrier, thus advantageously modified metal current-collector (example
Such as, copper foil).Energy needed for carrier gas is dissociated into excited ion by plasma offer is banged with providing the ion of metal collector
It hits, then carries out lithium metal, as discussed further below.Carrying out processing with plasma-based reducibility gas can play
One or more of function: cleaning current collector surface reduces metal oxide present on metal collector surface, enhancing profit
Moist and modified metal interface is to promote lithium metal.Metal interface can be with the side for the nucleation overpotential for overcoming lithium to deposit
Formula is modified, and increases surface energy, so as to improve the wetability of lithium.The clean surface of corona treatment enhances wetting
Property, and allow lithium to flow and be precipitated as film.Therefore, carrying out processing with plasma gas reduces on processing surface
Lithium metal nucleation overpotential.
Fig. 4 will be hereafter described in more detail, Fig. 4 shows such reduction.In fig. 4 it is shown that for packet
Containing some aspects according to the present invention formed lithium base cathode component the first battery (being indicated by curve 160) with comprising without
The performance of the second battery (being indicated by curve 162) of the lithium base cathode of any corona treatment compares (labeled as 150 voltage
(V) be labeled as 152 time (hour)).As can be seen that due in Fig. 4 in the short period (for example, close to abscissa value
34.5) inner curve 162 is higher than curve 160, so nucleation overpotential reduces, the difference between two curves indicates overpotential drop
It is low.For example, it is about 10% (the 2mV reduction/total overpotential of 20mV) that nucleation overpotential reduces at 34.5.In some aspects, and not
The comparison interface of plasma-treated metal collector with lithium metal is compared, and is handled with plasma gas and lithium metal
The nucleation current potential at the interface between metal collector, which reduces, is greater than or equal to 10%.
In some aspects, as will be further described herein, after being handled with Reductive plasma gas, gold
Belong to the contact angle on the processing surface of current-collector compared with the contact angle for the metal collector that unused plasma gas is handled
Reduced.In some aspects, in some aspects according to the present invention with Reductive plasma gas to metal collector
After surface is handled, the contact angle of processing surface after the treatment is alternatively less than or is equal to about less than or equal to about 10 °
It 9 °, is alternatively less than or equal to about 8 °, is alternatively less than or equal to about 7 °, is alternatively less than or equal to about 6 °, is alternatively less than
Or it is equal to about 5 °, and in some variations, it is alternatively less than or equal to about 4 °.This contact angle can be static contact angle,
It is middle to set on a surface and measure using the sessile drop measuring technique of 5 microlitres of drops.
In addition, the processing surface can have along processing and exposure after being handled with Reductive plasma gas
Surface existing for metal oxide of the quality less than or equal to about 10%, be alternatively less than or the metal equal to about 5 mass %
Oxide, be alternatively less than or equal to 4% mass metal oxide, be alternatively less than or the metal oxygen equal to about 3 mass %
Compound, and in some variations, is alternatively less than or the metal oxide equal to about 2 mass %.For example, this metal
Oxide can be measured from exposed surface towards interior zone with the depth of about 500nm.
After being handled with Reductive plasma gas metal collector surface, this method further includes having
Apply lithium metal to the processing surface of metal collector in the environment of minimum oxidation material.Oxidation material may include oxygen carrier,
Such as oxygen (O2), carbon monoxide (CO), carbon dioxide (CO2), nitrogen oxides (NOx), water (H2O) etc..In some variations,
Apply lithium environment be substantially free of be oxidation material specific compound or substance.Term " being substantially free of " mentioned herein
Refer to that compound or substance are few to the degree that undesirable and/or illeffects is negligible or is not present, to promote
Metal oxide is formed on current collector surface or undesirably reacts to form oxide with lithium metal.
In some aspects, it includes undesirable less than or equal to about 1 weight % for " being substantially free of " environment of such compound
Oxidation material is alternatively less than or is equal to about 0.5 weight %, is alternatively less than or is equal to about 0.1 weight %, and certain excellent
Choosing aspect is the undesirable oxidation material of 0 weight %.In some variations, total water capacity of the environment is less than or equal to about 1 weight
% is measured, about 0.5 weight % is alternatively less than or is equal to, is alternatively less than or is equal to about 0.1 weight %, and in certain preferred sides
Face, total water capacity in the environment are 0 weight %.Environment with minimum oxidation material or substantially free of oxidation material helps
In reduce or reduce apply when with high activity lithium generation it is undesirable react, this is handled with plasma gas with clear
It is not usually problem in typical process when clean metal (such as copper, nickel or steel), for example, for etching or cleaning.In some aspects,
Environment-before applying lithium metal during corona treatment-can also be substantially free of any oxidation material.
Processing step and application step can carry out in same reaction chamber.It, can be to metal current collection during applying technique
Device and/or lithium metal source apply heat.Lithium metal source and current-collector can be also compressed together under an applied pressure.It is appropriate to apply
Stressed method may include using roller, pressing plate, blade etc..Heating stepses and optional the step of applying pressure, are conducive to lithium gold
Category realizes good caking property and wettability on the processing surface of current-collector.
In some aspects, heating stepses and optional pressure apply step and can be greater than or equal in batch processing
It about 15 minutes, is optionally greater than or equal to about 20 minutes, is optionally greater than or equal to about 25 minutes, and in some variations,
It is optionally greater than or equal to about 30 minutes.In some aspects, heating and optional application pressure are sustainable greater than or equal to about 15
Minute to less than or be equal to about 60 minutes, be optionally greater than or equal to about 20 minutes to less than or be equal to about 45 minutes.Certain
Other aspects, heating stepses and optional pressure, which apply step, can carry out in batch processing greater than or equal to about 1 minute, can
Selection of land is optionally greater than or equal to about 10 minutes greater than or equal to about 5 minutes, and in some variations.Therefore, in continuous work
In skill, heating stepses and optional pressure apply step and can carry out greater than or equal to about 1 minute to less than or be equal to about 10 minutes.
Although the material that the suitable temperature of heating stepses depends on using as those skilled in the art will appreciate is (for example, take
Certainly in specific lithium ion source material and collector materials), but in some variations, heating stepses be temperature less than or equal to about
It is carried out at a temperature of 170 DEG C, be alternatively less than or equal to about 150 DEG C, be alternatively less than or be equal to about 125 DEG C, and at certain
In a little modifications, it is alternatively less than or equal to about 120 DEG C.In some variations, heating stepses can be greater than or equal to about 20 DEG C
(for example, about room temperature) to less than or equal to about 170 DEG C at a temperature of carry out, be optionally greater than or equal to about 50 DEG C at least below
Or be equal to about 150 DEG C, be optionally greater than or equal to about 50 DEG C to less than or be equal to about 125 DEG C, it is and in some variations, optional
Ground is greater than or equal to about 50 DEG C to less than or equal to about 120 DEG C.
It is compressed by applying external pressure or power to the lithium metal source being arranged in metal collector.In certain changes
In type, the amount of pressure applied can greater than or equal to about 0.1MPa (about 15psig) to less than or be equal to about 40MPa (about 5,
800psig), be optionally greater than or equal to about 10MPa (about Isosorbide-5-Nitrae 50psig) to less than or be equal to about 30MPa (about 4,
350psig), and in some variations, (about 2,900psig) about 20MPa.
On the one hand, after the treatment step and before applying step, metal collector may be provided on warm table.The heating
Platform can have above-mentioned temperature, be greater than or equal to about 50 DEG C to less than or equal to about 120 DEG C.In some aspects, it is applied to gold
The lithium metal for belonging to the processing surface of current-collector is lithium film or foil.When applying, lithium metal flows through and is attached to the processing surface, with
Form lithium layer.In some variations, this layer forms the lithium metal electroactive layer of cathode.In at least part phase for applying step
Between, if applying pressure to lithium metal source or layer, more flat and more evenly lithium metal layer can be formed, it can be in current collection
It is soaked on the processing surface of device, and is bonded to the processing surface of current-collector well.
In some variations, the method to form lithium an- ode is provided comprising use Reductive plasma gas pair
The surface of current-collector is handled, to reduce the nucleation overpotential for being used for lithium metal.With not plasma-treated current-collector
It is compared with the comparison interface of lithium metal, with the nucleation current potential at the interface between plasma gas and the current-collector of lithium metal processing
It can be reduced more than or equal to 10%, be optionally greater than or equal to 11%, be optionally greater than or equal to 12%, be optionally larger than or wait
In 13%, it is optionally greater than or equal to 14%, and in some variations, is optionally greater than or equal to 15%.
After the treatment step, the processing surface of the current-collector including copper has the contact angle less than or equal to about 10 °, and
And have less than or equal to about 5% Cu oxide or above-mentioned any value.It is according to the present invention in some terms, with reproducibility etc. from
Daughter gas carries out surface preparation to copper foil and film and provides on copper foil collector successfully deposit lithium metal and enhance
The ability at interface between copper and lithium metal, to provide the good long-term behaviour of the electrochemical cell with this cathode.
This method, which may also include, is heated to the copper-based current-collector with the processing surface greater than or equal to about 50 DEG C to small
In or equal to about 120 DEG C of temperature.This method may additionally include in the environment for be substantially free of oxide matter and be applied to lithium metal
The processing surface of metal collector.The water content of the environment may be less than or equal to about 1 weight % or above-mentioned any value.Lithium metal
It flows through and is attached on processing surface to form the layer for limiting electroactive material, to form lithium an- ode component.
In addition, metal collector can be thickness greater than or equal to about 2 microns (μm) to less than or the film equal to about 30 μm
Or foil.The lithium metal source or layer for being applied to the processing surface of metal collector can be lithium film or foil.In some aspects, lithium metal
The thickness of source or layer can greater than or equal to about 1 μm to less than or be equal to about 75 μm, be optionally greater than or equal to about 5 μm to less than or
Equal to about 75 μm, or in other respects, it is optionally greater than or equal to about 1 μm to less than or equal to about 50 μm.In the process of application
In, foil or film may soak and thinning on current-collector.
The thickness after applying step of lithium metal layer can be greater than or equal to about 20nm to less than or equal to about 100 microns of (μ
m).In some variations, the thickness for being applied to the lithium metal layer of metal collector greater than or equal to about 1 μm to less than or can be equal to
About 75 μm, and in some variations, it is optionally greater than or equal to about 1 μm to less than or equal to about 50 μm.
In some aspects, the Reductive plasma gas have as mentioned component component, it may for example comprise selected from by with
The molecule for the group that lower items are constituted: argon (Ar), nitrogen (N2), hydrogen (H2), ammonia (NH3), and combinations thereof.With reproducibility plasma
The step of body gas handles the surface uses the plasma source selected from the group being made of the following terms: by microwave etc.
Energetic plasma, the low pressure plasma, inductively coupled plasma of plasma source generation, and combinations thereof.Processing step and
Apply step to carry out in same reaction chamber.The step handled with surface of the Reductive plasma gas to metal collector
Suddenly the high energy plasma as caused by 13.56MHz radio frequency (RF) plasma source or 2.48GHz microwave plasma source can be used
Body carries out.In general, the high-energy of plasma means that the ion concentration in plasma is relatively high.Typical plasma
Have 10 in the plasma10cm3Ion.High energy plasma can have 1011cm3Ion (for example, comparing plasma
In ionic weight it is 10 times high).Power level compared with low energy plasma can be approximately greater than or equal to about 50W to less than or wait
In about 100W, because high power/high energy plasma power level can be greater than or equal to about 100W to less than or equal to about
5,000W(5KW)。
Referring now to Figure 1, Fig. 1 shows the plasma process system on the surface 18 for handling negative metal collector 20
10 example, but the component of various plasma process systems 10 and configuration can change.Activate plasma energy source 42
To generate plasma jet 24.In one example, any suitable plasma device can be employed as energy of plasma
Source 42.It include plasma energy source 42 in plasma-reaction-chamber 28.It should be noted that when using low pressure plasma system
When, plasma system needs to be located in hothouse or glove-box, to avoid being exposed in moisture and oxygen.Plasma
Body energy source 42 includes that plasma flame 36 (generates in plasma evaporation room 30, can be the combustion for flame 36
Burn or ionisation chamber) and hardened area 34 and cooling linkage 32.
In system 10, carrier gas 22 is delivered to plasma-reaction-chamber 28.The example of suitable carrier gas 22 includes going back Primordial Qi
Body, or the composition including reducing gas and inert gas.For example, carrier gas 22 may include Reductive plasma gas, tool
There is the redox molecule selected from the group being made of the following terms: hydrogen (H2), ammonia (NH3), and combinations thereof.Carrier gas 22 may also include
Inert molecule selected from the group being made of the following terms: argon (Ar), helium (He), nitrogen (N2), and combinations thereof.As an example,
Contain Ar-N2、N2-H2、Ar-H2And/or NH3The plasma of gas component can be used as carrier gas 22.It should be appreciated that other gases
(including other inert gases) also is used as carrier gas 22, as long as it is not oxidation material.Plasma flame 36 uses load
Gas 22 and power supply and formed, such as microwave, direct current (DC), alternating current (AC) or radio frequency (RF) in plasma evaporation room 30.
Although it is not shown, the electrode in plasma evaporation room 30 ionizes carrier gas 22, to form plasma jet 24.
Carrier gas 22 is delivered to plasma chamber 28 via conveying mechanism 26.Conveying mechanism 26 can be any suitable polymerization
Object, glass, stainless steel, copper or other types of pipe.Due to pressure difference, so the stream of carrier gas 22 is conveyed as gas source.
The temperature of plasma evaporation room 30 can be controlled by controlling the temperature of plasma flame 36.It can pass through
Microwave, direct current (DC), alternating current (AC) or radio frequency (RF) change/adjusting are attached to the power in plasma evaporation room 30 to control
The temperature of plasma flame 36 processed.In some aspects, plasma energy source 42 can be by microwave plasma source, low pressure
The high energy plasma that plasma, inductively coupled plasma and combinations thereof generate.
For example, the example of the parameter of adjustable plasma energy source 42 includes the generator class of plasma
Type, nozzle diameter, nozzle height, nozzle velocity, flow velocity, temperature, plasma potential, plasma current, plasma function
Rate and/or plasma circulation time.However, such parameter can be unrelated with all energy of plasma systems.For example,
When the system uses microwave plasma, nozzle is not used.On the contrary, plasma creates in a vacuum chamber.
In one example, be applied to the electrode (not shown) of plasma energy source 42 voltage range can be greater than or
Equal to about 130 volts to less than or equal to about 250 volts.In a variant, the temperature of plasma flame 36 is at about 500 DEG C
To in the range of about 5,000 DEG C, and the temperature of plasma evaporation room 30 is in the range of about 300 DEG C to about 1,000 DEG C.
Plasma flame 36 makes plasma jet 24 accelerate into hardened area 34, subsequently into cooling linkage
32.In hardened area 34 and cooling linkage, plasma jet 24 be exposed to than in plasma-reaction-chamber 28 etc.
The much lower temperature of gas ions flame temperature.The lower temperature can be equal to or less than environment temperature or room temperature (for example, being below about
22℃).This cools down plasma jet 24 before it handles the surface 18 of current-collector 20.
Therefore, plasma jet 24 is projected by plasma nozzle 37 towards the surface 18 on current-collector 20.It should
Understand, plasma nozzle 37 has all of the surface 18 for being suitable for that plasma jet 24 is effectively communicated to current-collector 20
The hole in region.As described above, and not all plasma process system all use plasma nozzle 37.In one example,
Plasma jet 24 is sprayed with the speed (raster velocity) for being up to about 20mm/ seconds from plasma nozzle 37.In addition, certain
In modification, the temperature of plasma jet 24 can be in the range of about 20 DEG C to about 100 DEG C.It should be appreciated that plasma is penetrated
The temperature and speed of stream 24 can contribute to high-energy atmospheric pressure plasma, react simultaneously with the surface 18 of current-collector 20
It is handled.
The end of plasma nozzle 37 and the distance between the surface 18 of current-collector 20 can be greater than or equal to about 1cm
To less than or be equal to about 50cm in the range of, be optionally greater than or equal to about 5cm to less than or be equal to about 10cm.Plasma is penetrated
Stream 24 can be guided to continuing at surface greater than or equal to about 1 minute, be optionally greater than or equal to about 2 minutes, optionally greatly
In or be equal to about 3 minutes, be optionally greater than or equal to about 4 minutes, be optionally greater than or equal to about 5 minutes, optionally greatly
In or be equal to about 6 minutes, be optionally greater than or equal to about 7 minutes, be optionally greater than or equal to about 8 minutes, be optionally larger than or
It equal to about 9 minutes, is optionally greater than or equal to about 10 minutes, is optionally greater than or equal to about 15 minutes, is optionally larger than or waits
It in about 20 minutes, is optionally greater than or equal to about 25 minutes, and in some variations, is optionally greater than or equal to about 30 points
Clock.
As described above, high energy plasma is with high voltage and/or high-frequency and therefore with electronics and freely former
The plasma of the higher energy of son.In some variations, corona treatment can have greater than or equal to about 50W to less than or
Equal to the power level of about 5,000W, and it can carry out greater than or equal to about 1 minute to less than or be equal to about 10 minutes.Wait from
Daughter processing be high-energy processing in the case where, power level can greater than or equal to about 100W to less than or be equal to about 5,
000W, and can carry out greater than or equal to about 1 minute to less than or be equal to about 10 minutes.On the one hand, with reproducibility etc. from
The step of daughter gas handles the surface 18 of metal collector 20 can be with by 13.56MHz radio frequency (RF) plasma
Energetic plasma caused by source or 2.48GHz microwave plasma source carries out.
After the surface 18 to current-collector 20 is handled, plasma energy source 42 can be activated to stop generating etc.
Gas ions jet stream 24.As shown in Figure 1, processed current-collector 20 is arranged on warm table (not shown), wherein can pass through collection
Electric appliance 20 applies heat towards processing surface 18.Next, for example, staying in plasma-reaction-chamber in processed current-collector 20
When in 28, lithium metal source be may be provided on processing surface 18.By at high surface energy quantity set electric appliance (for example, processed copper foil)
Lithium metal can be deposited as required thickness by upper fusing.The clean surface of corona treatment (for example, processed copper foil)
Wetability is enhanced, and allows lithium to flow and is precipitated as film.As described above, plasma-reaction-chamber 28 is during applying technique
It is substantially free of oxide matter.
Can be the lithium metal layer such as film or foil lithium metal source can on the surface 18 for be placed on current-collector 20 it
Before cleaned.Lithium metal is relatively soft, and as described above, has high reaction activity, especially for oxidation material.Cause
This, carrying out sandblasting with loose and hard grinding agent may be not suitable for cleaning lithium metal source.In view of the reactivity of lithium metal,
It equally can be to avoid proton solvent (for example, ethyl alcohol, acetone, ether etc.) in cleaning or processing.As non-limiting example, properly
Cleaning procedure may include with aprotic solvent (for example, hexane) wipe surface, or use other temperature known in the art
The clean technologies that avoid and the lithium of sum react.
Referring now to Fig. 2, Fig. 2 shows the lithium base cathode 50 by being formed according to the method for the present invention.Lithium base cathode 50
Including having the negative metal collector 52 of processing surface region 54.In some variations, current-collector 52 is that thickness is greater than or equal to
About 2 μm to less than or film or foil equal to about 30 μm.The thickness of processing surface region 54 depends on passing through for plasma jet
Times and duration, this depends, at least partially, on the plasma process parameters during processing step.In this way, can use
Several times of plasma body is sprayed to realize that the metal oxide by certain level is removed to required thickness, and is ensured required at nuclear power
Potential drop low-level and surface energy modifiers/contact angle reduce.In one example, the thickness for handling surface region 54 can be big
In or be equal to about 1 micron to less than or be equal to about 20 microns in the range of.
Lithium metal source or lithium metal layer 60 are arranged in the processing surface region 54 of negative metal collector 52.It is applied to current collection
The lithium metal layer 60 of the processing surface region 54 of device 52 can be the thickness before applying step greater than or equal to about 5 μm to small
In or equal to about 75 μm of lithium film or foil.As noted previously, as carried out on current collector surface (for example, processed copper foil) etc.
Gas ions processing, so nucleation overpotential reduces and the enhancing of the wetability of lithium, so that lithium can be used as liquid film flow and deposition.
When applying lithium metal layer 60 during technique, the thickness of lithium metal layer 60 is smaller than the thickness in situ after electrochemical cell circulation,
Because supplemental lithium present in positive electrode or electrolyte can be plated on lithium metal layer 60.Therefore, lithium metal layer 60 can be
Thin initiation oxidant layer or shock plate layer, to promote the subsequent growth of lithium, (it is from the active material and/or electrolyte in electrochemical cell
Migration).
Therefore, the present invention covers electrochemical cell comprising the lithium base cathode component formed by the above method.The lithium base
Cathode includes metal collector, which includes the metal selected from the group being made up of: copper (Cu), nickel (Ni), iron
(Fe) and combinations thereof, surface is handled with Reductive plasma gas.Lithium base cathode further includes negative electricity active layer,
It includes the lithiums being arranged on metal collector surface.Electrochemical cell may also include anode, diaphragm and packet electrolysis containing lithium salt
Matter.In some aspects, electrochemical cell be able to maintain its charging capacity at least 85% (initial charge and discharge cycles it
Persistently it is greater than or equal to operation at least about 500 hours afterwards).
By the specific embodiment that includes herein it will be further appreciated that the various embodiments of the technology of the present invention.Tool is provided
Body embodiment be in order to illustrate how to make and use according to this teaching composition, device and method, unless otherwise specifically
Bright, otherwise method according to this teaching is not intended to show the given embodiment for or being also manufactured without or testing of the invention.
Example A
In one example, lithium base cathode is prepared according to certain aspects of the invention as described below.It can be from
Size commercially available from Hoshen is 100mm × 100mm, is used as current-collector with a thickness of 10 microns (μm) of copper foils.Copper foil is imported and is passed through
The reaction chamber of the plasma reactor of high energy plasma is generated by 2.48GHz microwave plasma source P400.Reaction chamber
Full of argon gas, and in the vacuum of oxide-free matter.To have 50sccm Ar and 10sccm H2The H of ratio2/ Ar composition
Reproducibility carrier gas be introduced into the reaction chamber of plasma reactor.For microwave plasma, nozzle is not used.Deng from
Daughter generation is carried out at 300W in the vacuum chamber with air-flow as described above, and time range was greater than or equal to about 1 minute
To less than or it is equal to about 10 minutes.Power can be greater than or equal to about 50W to less than or equal to about 500W.In this way, copper
The surface of foil is pre-processed with Reductive plasma gas, to enhance the reduction of nucleation overpotential, reduces Cu oxide, and
The ability of enhancing and lithium metal bonding.
Sample is prepared for XPS analysis, (y-axis labeled as 100 is atom with depth curve as shown in Figure 3
Concentration (%), and the x-axis labeled as 110 is sputter depth (nm)).After with Microwave plasma treatment copper foil, thickness is used
About 200 nanometers of graphite carbon-coating coating, to protect the interface for XPS processing.Oxygen 1S is labeled as 112, and copper 2P is labeled as
114, carbon 1S are labeled as 116.As can be seen that about 500nm sputter depth hereinafter, representing the original of the oxygen 112 of metal oxide
Sub- concentration is below about 5%.
Also measurement contact angle to compare the copper collector before and after being handled with plasma deoxidization gas, with
Enhancing/reduction of display surface energy, which improve the wetabilitys and caking property of the copper foil of corona treatment and lithium metal.This
Contact angle can be static contact angle, wherein being set on the surface and being surveyed using the sessile drop measuring technique of 5 microlitres of drops
Amount.Before what processing step in office, copper foil has about 58 ° of contact angle.After above-mentioned corona treatment, the processing of copper foil
Surface has the contact angle less than 10 °.
Example B
With Reductive plasma gas in the reaction chamber of 2.48GHz microwave plasma reactor described in example A
After body handles copper foil, stops introducing reproducibility carrier gas and generate plasma.By plasma-treated current-collector
It is arranged on the platform for being heated to about 50 DEG C.Can from the commercially available size of Fu Meishi company (FMC Lithium) be 25mm ×
25mm and it is used as the lithium metal source of electroactive material layer of being formed with a thickness of the lithium foil of 1mm.Lithium foil is unprocessed, and in reaction chamber
It is provided in inert atmosphere and (fills argon gas and be free of any oxidation material).Make the corona treatment table of lithium foil and copper collector
Face contact is placed on the copper foil of heating with forming sample A. for lithium, and starts to flow.Do not apply pressure in this example.
Example C
With use Reductive plasma gas carry out pretreated surface and to its apply lithium metal sample A as
First electrode includes into the first battery testing Li//Cu battery.First battery is the button cell that capacity is about 1mAh.Counterelectrode
It is lithium metal foil (thickness is about 250 μm).Electrolyte includes 1M LiTFSI-DME:DIOX (v:v 1:1), wherein 2%LiNO3
As additive, diaphragm is arranged between cathode and counterelectrode.
Comparative examples D
It the use of the size commercially available from Hoshen is 12.5mm, with a thickness of the current-collector (comparison as a comparison of 18 μm of copper foils
Sample B).It is incorporated to contrast sample B as first electrode in the second battery testing battery, is not necessarily to any pretreatment.Counterelectrode is
Lithium self-supporting metal foil, with a thickness of 250 μm.It by processing, not can be used as counterelectrode.Electrolyte includes 1M LiTFSI-
DME:DIOX (v:v1:1), wherein 2%LiNO3As additive, diaphragm is arranged between cathode and counterelectrode.It is followed for the first time
During ring, the lithium from counterelectrode is plated on untreated copper collector.
Example E
Fig. 3 compared the first battery testing battery with sample A and the second battery testing battery with contrast sample B
The voltage performance of charging and discharging over time.First battery and the second battery are the button cells that capacity is about 1mAh.
Li//Cu button cell is recycled 4 hours at 25 DEG C with the charge/discharge rates of 250 μ A.In Fig. 4, y- axis is labeled as 150
Voltage (V), and x-axis is the time (hour) labeled as 152.Sample A is labeled as 160, and contrast sample B is labeled as 162.It can
To find out, the voltage performance of sample A (160) (by the copper collector of corona treatment) improves over time,
Because entire voltage platform phase relatively flat, this shows the copper foil for sample A compared with the performance of (162) contrast sample B
There is smooth lithium platingactive.In addition, compared with untreated contrast sample B, the first time of the Cu of the corona treatment of sample A
Lithium removing/plating cycle is higher, i.e., and 96.2% pair 95.9%.
The foregoing description of embodiment is provided for the purpose of illustration and description.It is not intended to exhaustion or limitation originally
The present invention.The each element or feature of specific embodiment is generally not limited to this particular embodiment, but is under applicable circumstances
It is interchangeable, and can be used in selected embodiment, even if being not shown or described in detail.It equally can also be with a variety of sides
Formula variation.These modifications should not be considered as to the disengaging present invention, and all these modifications are intended to and are included in the scope of the present invention
Within.
Claims (10)
1. a kind of method for being used to form lithium base cathode, which comprises
It is handled with surface of the Reductive plasma gas to metal collector, so that after the processing step, institute
State metal collector processing surface be formed to have contact angle less than or equal to about 10 ° and have less than or equal to about
5% metal oxide, wherein the metal in the metal collector is selected from the group being made of the following terms: copper (Cu), nickel
(Ni), iron (Fe) and combinations thereof；And
Lithium metal is applied to the processing surface of the metal collector in the environment for being substantially free of oxide matter,
In, the lithium metal flows through and is attached to the processing surface, with formed thickness greater than or equal to about 1 micron (μm) to less than or
Lithium layer equal to about 75 μm, to form the lithium base cathode.
2. the method for claim 1, wherein the Reductive plasma gas includes selected from by the following terms institute structure
At group molecule: argon (Ar), nitrogen (N2), hydrogen (H2), ammonia (NH3) and combinations thereof.
3. the method for claim 1, wherein being handled with the Reductive plasma gas the surface
The step uses the plasma source selected from the group being made of the following terms: the high energy etc. generated by microwave plasma source
Gas ions, low pressure plasma, inductively coupled plasma, and combinations thereof.
4. described the method for claim 1, wherein after the processing step and before the application step
Metal collector be arranged in temperature greater than or equal to about 50 DEG C to less than or the warm table equal to about 120 DEG C on.
5. the method for claim 1, wherein the processing step and the application step in same reaction chamber into
Row.
6. the method for claim 1, wherein with Reductive plasma gas to the surface of metal collector into
The step of row processing is with as caused by 13.56MHz radio frequency (RF) plasma source or 2.48GHz microwave plasma source
Energetic plasma carries out.
7. the method for claim 1, wherein the metal collector be thickness greater than or equal to about 2 microns to less than
Or film or foil equal to about 30 microns, and the lithium metal for being applied to the processing surface of the metal collector is thick
Degree is greater than or equal to about 5 μm to less than or lithium film or foil equal to about 75 μm.
8. the method for claim 7, wherein during described at least part for applying step, Xiang Suoshu lithium layer is applied
Plus-pressure.
9. a kind of method for being used to form lithium an- ode, which comprises
The surface of current-collector for including copper is handled with Reductive plasma gas so that the processing step it
Afterwards, the processing surface of the current-collector has the contact angle less than or equal to about 10 °, and has less than or equal to about 5%
Cu oxide；
The current-collector with the processing surface is heated to greater than or equal to about 50 DEG C to less than or equal to about 120 DEG C
Temperature；And
It is being substantially free of oxide matter and is being applied to lithium metal in environment of the water content less than or equal to about 1 mass % described
The processing surface of current-collector, wherein the lithium metal flows through and is attached to the processing surface, with formed thickness be greater than or
Equal to about 1 micron (μm) to less than or the lithium layer equal to about 75 μm, to form the lithium an- ode.
10. method as claimed in claim 9, wherein the processing step and the application step in same reaction chamber into
Row, and the step handled with the surface of the Reductive plasma gas to metal collector with by
Energetic plasma caused by 13.56MHz radio frequency (RF) plasma source or 2.48GHz microwave plasma source carries out.
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| US15/886,396 US11196045B2 (en) | 2018-02-01 | 2018-02-01 | Plasma pretreatment on current collectors for thin film lithium metallization |
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| CN114171712A (en) * | 2021-11-12 | 2022-03-11 | 天津中能锂业有限公司 | Method for improving lithium supplement on surface of negative electrode, negative electrode for lithium supplement and lithium ion secondary battery |
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